[0001] The present invention relates to new metallocene catalysts for use in preparation
of olefin or styrene polymers and polymerization methods using the metallocene catalysts.
More specifically, the present invention relates to new metallocene catalysts which
are capable of preparing olefin or styrene polymers having a high activity, a good
stereoregularity, a high melting point, and a good molecular weight distribution in
the presence of a small amount of a co-catalyst. The present invention also relates
to polymerization method for preparing such olefin or styrene polymers using the metallocene
catalysts.
[0002] Olefin or styrene polymers are generally prepared by radical polymerization, ionic
polymerization, or coordination polymerization using a Ziegler-Natta catalyst. Radical
or ionic polymerization provides olefin or styrene polymers having mainly an atactic
structure. Coordination polymerization using a Ziegler-Natta catalyst provides olefin
or styrene polymers having mainly an isotactic structure.
[0003] The polymers are structurally divided into three groups such as atactic polymers,
isotactic polymers, and syndiotactic polymers, depending on the position of benzene
rings as a side chain in relation to a main chain of molecular structure of the polymers.
An atactic structure means that configuration of side chains is irregular. An isotactic
structure means that side chains are positioned at one side relative to a main chain.
A syndiotactic structure means that side chains are alternatively arranged for a main
chain.
[0004] The polymers having a syndiotactic structure have been only theoretically known,
and practically not prepared until a metallocene catalyst was employed to the preparation
methods.
[0005] Development of the metallocene catalysts was to provide a syndiotactic polystyrene
having a stereoregularity or polyolefins having improved physical properties. The
conventional metallocene catalysts have a structure which a Group IV transition metal
compound of the Periodic Table of Elements is coordinated with ligands composed of
one or two cycloalkanedienyl groups or their derivatives. The Group IV transition
b metal of the Periodic Table of Elements contain titanium, zirconium, hafnium, etc.
The cycloalkanedienyl groups include a cyclopentadienyl group, an indenyl group, a
fluorenyl group, etc.
[0006] The metallocene catalysts are usually employed with a co-catalyst. The conventionally
used Ziegler-Natta catalysts system is composed of a halogenated titanium compound
as a main catalyst and alkylaluminium as a co-catalyst. Example of the halogenated
titanium compound is titanium tetrachloride. Example of alkylaluminium is trimethylaluminium
and triethylaluminium.
[0007] While, recently developed metallocene catalyst system is employed with alkylaluminoxane
as a co-catalyst, which is capable of preparing polystyrenes having a stereoregularity
or polyolefins having improved physical properties. Alkylaluminoxane is produced by
reacting alkylaluminium with H
2O. Especially, syndiotactic polystyrene has a structure which benzene rings as a side
chain is alternatively positioned relative to a main chain of the polymer. The syndiotactic
polystyrene has an excellent heat-resistance and physical properties since the polymer
has about 270°C of a melting point (T
m) due to stereoregularity comparing with the conventional amorphous atactic polystyrene,
which is of interest.
[0008] European Patent Publication No. 210 615 A2 (1987) discloses a syndiotactic polystyrene
having a stereoregularity. Also, the patent discloses cyclopentadienyltitanium trichloride
and an alkyl-substituted cyclopentadienyltitanium trichloride such as pentamethylcyclopentadienyltitanium
trichloride to prepare syndiotactic polystyrenes. It is known that the metallocene
catalysts have a good activity, molecular weight distribution, and syndiotactic index.
[0009] US Patent No. 4,544,762 discloses a preparation method of aluminoxane which can be
used as a component of catalysts in the preparation of highly active and homogeneous
Ziegler-Natta catalysts.
[0010] US Patent No. 5,026,798 discloses a process for polymerizing α-olefins which utilize
certain monocyclopentadienyl metal compounds of a Group IVb transition metal of the
Periodic Table of Elements in an aluminoxane activated catalyst system to produce
crystalline poly-α-olefins.
[0011] US Patent Nos. 08/844,109 and 08/844,110 disclose a new alkyl bridged binuclear metallocene
catalyst (ABBM), silyl bridged binuclear metallocene catalyst (SBBM), and alkyl-silyl
bridged binuclear metallocene catalyst (A-SBBM) for preparing a syndiotactic polystyrene
having a high activity, a good stereoregularity, a high melting point, and a good
molecular weight distribution.
[0012] Accordingly, the present inventors have developed new metallocene catalysts for use
in preparation of olefin or styrene polymers and polymerization methods for effectively
preparing such olefin or styrene polymers using the metallocene catalysts.
[0013] An object of the present invention is to provide metallocene catalysts which are
capable of preparing olefin or styrene polymers having a high activity, a good stereoregularity,
a high melting point, and a good molecular weight distribution.
[0014] Another object of the present invention is to provide highly active metallocene catalysts
which are capable of preparing a large amount of olefin or styrene polymers in the
presence of a small amount of a co-catalyst.
[0015] A further object of the present invention is to provide preparation methods of metallocene
catalyst and polymerization methods for effectively preparing olefin or styrene polymers
using the metallocene catalysts.
[0016] Other objects and advantages of this invention will be apparent from the ensuing
disclosure and appended claims.
[0017] The new metallocene catalysts according to the present invention are prepared by
reacting a metallocene compound with a compound having at least two functional groups.
The metallocene compound is a transition metal compound which a transition metal is
coordinated with a main ligand such as cycloalkanedienyl group and an ancillary ligand.
Functional groups in the compound having at least two functional groups are selected
from the group consisting of a hydroxy group, a thiol group, a primary amine group,
a secondary amine group, etc.
[0018] The metallocene catalysts of the present invention can be prepared by reacting a
metallocene compound with a dianion compound produced by reacting an alkali metal
compound with a compound having those functional groups.
[0019] The metallocene catalysts according to the present invention have a structure which
an ancillary ligand of a metallocene compound is bonded to the functional groups of
a compound having at least two functional groups. A structure of the metallocene catalysts
can be varied according to the type of metallocene compounds, the type of the compound
having at least two functional groups, and the molar ratio of each reactant.
[0020] The metallocene catalyst is employed with a co-catalyst for styrene or olefin polymerization.
The co-catalyst is an organometallic compound or a mixture of non-coordinated Lewis
acid and alkylaluminium as it is widely known. The organometallic compound is usually
alkylaluminoxane or organoaluminium compound.
[0021] The syndiotactic polystyrenes or polyolefins having high physical properties are
prepared by using the catalyst system composed of a metallocene catalyst according
to the present invention and a co-catalyst. The monomers for polymerization include
styrene, styrene derivatives, or a compound having ethylenically unsaturated double
bonds. Those compounds are homopolymerized or copolymerized to give polystyrene or
polyolefin having a high activity, a good stereoregularity, a high melting point,
and a good molecular weight distribution.
[0022] The metallocene catalyst according to the present invention is prepared by reacting
a metallocene compound with a compound having at least two functional groups. The
metallocene catalyst has a structure which an ancillary ligand of a metallocene compound
is coordinated with a functional group of a compound having at least two functional
groups.
[0023] The metallocene compound of the present invention is represented by the following
general formulae (A) or (B). The compound having at least two functional groups is
represented by the following general formulae (C), (D), or (E).
MR
1aR
2bR
3cR
44-(a+b+c) (A)
MR
1dR
2eR
33-(d+e) (B)
T
2 -YR
5Y'-T
1 (C)
wherein M in the formulae (A) and (B) represents a transition metal of a Group IV,
V or VI of the Periodic Table and preferably of a Group IV such as titanium, zirconium
or hafnium; R
1, R
2, R
3 and R
4 are respectively a hydrogen atom; a halogen atom; an alkyl group, a cycloalkyl group
or an alkoxy group of C
1-20; an aryl group, an alkylaryl group or an arylalkyl group of C
6-20; a cyclopentadienyl group; a substituted cyclopentadienyl group; an indenyl group;
a substituted indenyl group; a fluorenyl group; or a substituted fluorenyl group;
a, b and c are respectively an integer of 0 to 4; and d and e are respectively an
integer of 0 to 3.
T1, T2, T3 and T4 in the formulae (C), (D) and (E) respectively represent a hydrogen atom; an alkyl
group, a cycloalkyl group or an alkoxy group of C1-20; an aryl group, an alkylaryl group or an arylalkyl group of C6-20; or an alkali metal such as Na, Li, K, etc.; Y, Y', Y'' and Y''' are respectively
O, S, -Nr17 or -Pr18 (wherein r17 and r18 are respectively an hydrogen atom; an alkyl group, a cycloalkyl group or an alkoxy
group of C1∼10; or an aryl group, an alkylaryl group or an arylalkyl group of C6-20); R5, R6, R7 and R8 are respectively R', R'-m-R'' or
(wherein R', R'', R''' and R'''' are respectively a linear alkyl group or a branched
alkyl group of C6∼20; a cycloalkyl group or a substituted cycloalkyl group of C3∼20; or an aryl group, an alkylaryl group or an arylalkyl group of C6∼40; r19 is a hydrogen atom; an alkyl group, a cycloalkyl group or an alkoxy group of C1∼10; or an aryl group, an alkylaryl group or an arylalkyl group of C6∼20); and m is an oxygen atom, a sulfur atom, -Nr17, -Pr18 or Sir17r18 (wherein r17 and r18 are respectively a hydrogen atom; an alkyl group, a cycloalkyl group or an alkoxy
group of C1-10; or an aryl group, an alkylaryl group or an arylalkyl group of C6∼20);
Q is N or -Cr20 (r20 is an alkyl group, a cycloalkyl group or an alkoxy group of C1∼10; or an aryl group, an alkylaryl group or an arylalkyl group of C6∼20); and
Z is C, Si, Ge or
[0024] The representative examples of the metallocene catalysts according to the present
invention are represented by the following general formulae (I)∼(V):
wherein M, M', M'' and M''' in the general formulae (I)∼(V) are respectively a transition
metal of a Group IV, V, or VI of the Periodic Table and preferably of a Group IV such
as titanium, zirconium or hafnium;
Cp, Cp', Cp'' and Cp'''are respectively a cyclopentadienyl group, an indenyl group,
a fluorenyl group or a derivative of each group which forms η5-bond with a transition metal such as M, M', M'' and M''' also, Cp, Cp', Cp'' and
Cp''' are represented by the general formulae (a), (b), (c) or (d);
(wherein r1, r2, r3, r4, r5, r6, r7, r8, r9, r10, r11, r12, r13, r14, r15 and r16 are respectively a hydrogen atom; an alkyl group, a cycloalkyl group or an alkoxy
group of C1∼20; or an aryl group, an alkylaryl group or an arylalkyl group of C6∼20; and f is an integer of 4 to 8.)
X1, X2, X3, X4, X5, X6, X7, X8, X9, X10, X11 and X12 are respectively a hydrogen atom; a hydroxy group; a halogen atom; an alkyl group,
a cycloalkyl group or an alkoxy group of C1∼20; or an aryl group, an alkylaryl group or an arylalkyl group of C6∼40;
G, G' and G'' are the groups connecting between two transition metals and are represented
as -YR5Y'- or T2-YR5Y'-T1 (wherein T1 and T2 represent respectively a hydrogen atom; and alkyl group, a cycloalkyl group or an
alkoxy group of C1-20; or an aryl group, an alkylaryl group or an arylalkyl group of C6-20);
Y, Y', Y'' and Y''' are respectively O, S, -Nr17 or -Pr18 (wherein r17 and r18 are respectively a hydrogen atom; an alkyl group, a cycloalkyl group or an alkoxy
group of C1-10; or an aryl group, an alkylaryl group or an arylalkyl group of C6-20); and
R5, R6, R7 and R8 are R', R'-m-R''
or (wherein R', R', R''' and R'''' are respectively a linear alkyl group or a branched
alkyl group of C6-20; a cycloalkyl group or a substituted cycloalkyl group of C3-20; or an aryl group, an alkylaryl group or an arylalkyl group of C6-40; r19 is the same as r17 or r18; and m is an oxygen atom, a sulfur atom, -Nr17, -Pr18 or Sir17r18 (wherein r17 and r18 are respectively a hydrogen atom; or an alkyl group, a cycloalkyl group or an alkoxy
group of C1-10; or an aryl group, an alkylaryl group or an arylalkyl group of C6∼20));
Q is N or -Cr20 (wherein r20 is a hydrogen atom; an alkyl group, a cycloalkyl group or an alkoxy group of C1∼10; or an aryl group, an alkylaryl group or an arylalkyl group of C6∼20); and
Z is C, Si, Ge or
[0025] A metallocene compound used for preparing the metallocene catalyst according to the
present invention is commercially available. Also, the metallocene compound may be
prepared according to a method which is conventionally well known. The metallocene
compound can be prepared by the steps comprising; preparing a salt of a substituted
cyclopentadienyl ligand containing alkali metal by reacting the corresponding cyclopentadienyl
ligand with an alkali metal or an alkali metal compound, introducing a silicon compound
or tin compound to the salt of a substituted cyclopentadienyl ligand, and reacting
the above resultant compound with a Group IV transition metal compound.
[0026] In case of substituting an ancillary ligand of a metallocene compound with an alkoxy
group, an alkyl group, or any other groups, the metallocene compound is reacted with
the desired equivalent of alcohol or alkyl metal compound. The above-described method
for preparing a metallocene compound may be easily performed by an ordinary skilled
person in the art.
[0027] The alkali metals or alkali metal compounds include K, Na,
n-butyllithium,
sec-butyllithium,
tert-butyllithium, methyllithium, sodium methoxide, sodium ethoxide, etc.
[0028] The Group IV transition metal compound of the Periodic Table of Elements include
titanium tetrachloride, zirconium tetrachloride, and hafnium tetrachloride.
[0029] The representative examples of the metallocene compound represented by the general
formula (A) or (B) include: pentamethylcyclopentadienyltitanium trichloride, pentamethylcyclopentadienylmethoxytitanium
dichloride, pentamethylcyclopentadienyldimethoxytitanium monochloride, 1,2,3,4-tetramethylcyclopentadienyltitanium
trichloride, 1,2,3,4-tetramethylcyclopentadienylmethoxytitanium dichloride, 1,2,3,4-tetramethylcyclopentadienyldimethoxytitanium
monochloride, 1,2,4-trimethylcyclopentadienyltitanium trichloride, 1,2,4-trimethylcyclopentadienylmethoxytitanium
dichloride, 1,2,4-trimethylcyclopentadienyldimethoxytitanium monochloride, 1,2,-dimethylcyclopentadienyltitanium
trichloride, 1,2,-dimethylcyclopentadienylmethoxytitanium dichloride, 1,2,-dimethylcyclopentadienyldimethoxytitanium
monochloride, methylcyclopentadienyltitanium trichloride, methylcyclopentadienylmethoxytitanium
dichloride, methylcyclopentadienyldimethoxytitanium monochloride, cyclopentadienyltitanium
trichloride, cyclopentadienylmethoxytitanium dichloride, cyclopentadienyldimethoxytitanium
monochloride, pentamethylcyclopentadienylmethyltitanium dichloride, pentamethylcyclopentadienyldimethyltitanium
monochloride, 1,2,3,4-tetramethylcyclopentadienylmethyltitanium dichloride, 1,2,3,4-tetramethylcyclopentadienyldimethyltitanium
monochloride, 1,2,4-trimethylcyclopentadienylmethyltitanium dichloride, 1,2,4-trimethylcyclopentadienyldimethyltitanium
monochloride, 1,2-dimethylcyclopentadienylmethyltitanium dichloride, 1,2-dimethylcyclopentadienyldimethyltitanium
monochloride, methylcyclopentadienylmethyltitanium dichloride, methylcyclopentadienyldimethyltitanium
monochloride, cyclopentadienylmethyltitanium dichloride, and cyclopentadienyldimethyltitanium
monochloride.
[0030] The representative examples of the compound having at least two functional groups
represented by the general formulae (C), (D) or (E) include: ethylene glycol, 1,3-propanediol,
1,2-propanediol, (s)-(+)-1,2-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol,
2-ethyl-2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol,
2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, (R)-(-)-1,3-butanediol, (S)-(+)-1,3-butanediol,
(±)-1,2-butanediol, 2,3-butanediol,
meso-2,3-butanediol, (2R,3R)-(-)-2,3-butanediol, (2S,3S)-(+)-2,3-butanediol, 3,3-dimethyl-1,2-butanediol,
pinacol, 1,5-pentanediol, 1,4-pentanediol, 1,2-pentanediol, 2,4-pentanediol, (2R,4R)-(-)-pentanediol,
(2S,4S)-(+)-pentanediol, 2-methyl-2,4-pentanediol, (R)-(-)-2-methyl-2,4-pentanediol,
2,4-dimethyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,5-hexanediol,
(±)-1,2-hexanediol, 2,5-hexanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol,
1,7-heptanediol, 1,8-octanediol, 1,2-octanediol, 1,9-nonanediol, 1,10-decanediol,
1,2-decanediol, 1,12-dodecanediol, (±)-1,2-dodecanediol,
cis-1,2-cyclopentanediol,
trans-1,2-cyclopentanediol, 1,3-cyclopentanediol,
trans-1,2-cyclohexanediol, 1,2-cyclohexanediol, 1,4-cydohexanediol, 2,5-dimethylcyclohexane-1,4-diol,
2,5-isopropylcyclohexane-1,4-diol,
cis-1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, (+)-
cis-
p-methane-3,8-diol, (-)-
trans-
p-methane-3,8-diol, (±)-
trans-1,2-cycloheptanediol,
cis-1,2-cyclooctanediol,
trans-1,2-cyclooctanediol, 1,4-cyclooctanediol,
cis-1,5-cyclooctanediol, 4,8-bis(hydroxymethyl)tricyclo[5.2.1.02,6]-decane, (1R,2R,3S,5R)-(-)-pinandiol,
1,5-decalindiol, 3-cyclohexane-1,1-dimethanol, (±)-
trans-2-cyclohexane-1,4-diol,
trans-
p-ment-6-ene-2,8-diol,
cis-3,5-cyclohexadiene, 5-norbonene-2,2-dimethanol, (±)-(2-
endo,3-
exo)-bicyclo[2.2.2]-oct-5-ene-2,3-dimethanol, 1,1,1-tris(hydorxymethyl)ethane, (R)-(+)-1,2,4-butanetriol,
(S)-(-)-1,2,4-butanetriol, 2-ethyl-2-(hydroxymethyl)-1,3-propanediol, (±)-1,2,3-trihydroxyhexane,
1,2,6-trihydroxyhexane, ethanolamine, 2-hydroxyethylhydrazine, 3-amino-1-propanol,
DL-1-amino-2-propanol, 4-amino-1-butanol, (±)-2-amino-1-butanob, 5-amino-1-pentanol,
DL-2-amino-1-pentanol, 6-amino-1-hexanol, 2-(2-aminoethoxy)ethanol, 2-(methylamino)ethanol,
2-(ethylamino)ethanol, 2-(propylamino)ethanol, diethanolamine, diisopropanolamine,
2-(butylamino)ethanol, N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine,
triethanolamine, triisopropanolamine, 1-[N,N-bis(2-hydroxyethyl)amino]-2-propanol,
catechol, 3-methylcatechol, 4-methylcatechol, 4-
tert-butylcatechol, DL-3,4-dihydroxyphenylglycol, 3,5-diisopropylcatechol, 3,5-di-
tert-butylcatechol, resorcinol, 2-methylresorcinol, 4-ethyiresorcinol, 4-hexylresorcinol,
4-dodecylresorcinol, 5-pentylresorcinol, 5-pentadecylresorcinol, 2,5-dimethylresorcinol,
hydroquinone, methylhydroquinone,
tert-butylhydroquinone, 2,3-dimethylhydroquinone, 2,5-di-
tert-butylhydroquinone, 2,5-bis(1,1,3,3-tetramethylbutyl)hydroquinone, trimethylhydroquinone,
1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene,
1,6-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene,
bis(2-hydroxyphenyl)methane, (±)-hydrobenzoin,
meso-hydrobenzoin, (R,R)-(+)-hydrobenzoin, (S,S)-(-)-hydrobenzoin, benzopinacole, 1,4-benzenedimethanol,
α,α,α',α'-tetramethyl-1,4-benzenedimethanol, 1,5-dihydroxy-1,2,3,4-tetrahydronaphthalene,
2,2'-biphenyldimethanol, 3-(3,5-di-
tert-butyl-4-hydroxyphenyl)-1-propanol, (±)-1-phenyl-1,2-ethanediol, (S)-(+)-1-phenyl-1,2-ethanediol,
(R)-(-)-1-phenyl-1,2-ethanediol, (R)-(+)-1,1,2-triphenyl-1,2-ethanediol, 4,4'-biphenol,
phenylhydroquinone, bis(4-hydroxyphenyl)methane, 4,4'-isopropylidenediphenol, 4,4'-(1,4-diisopropylidenediphenol),
2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1,1-tri(4-hydroxyphenyl)ethane, meso-hexestrol,
1,2-ethanedithiol, 1,3-propanedithiol, 1,2-propanedithiol, 1,4-butanedithiol, 1,3-butanedithiol,
1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 2-mercaptoethanol,
1-mercapto-2-propanol, 3-mercapto-2-butanol, n 3-mercapto-1,2-propanediol, 2,3-dimercapto-1-propanol,
dithiothreitol, dithioerythreitol, 2-mercaptoethyl ether, 1,4-dithiane-2,5-diol, 2,5-dimethyl-2,5-dihydroxy-1,4-dithiane,
1,5,9,13-tetrathiacyclohexadecane-3,11-diol, 1,5,9,13,17,21-hexathiacyclotetracosane-3,11,19-triol,
ethyleneamine, 1,3-diaminopropane, 1,2-diaminopropane, 1,4-diaminobutane, 1,2-diamino-2-methylpropane,
1,6-hexanediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 2,5-dimethyl-2,5-hexanediamine,
1,9-diaminononane, 1,10-diaminodecane, 1,12-diaminododecane, spermidine, 4,4'-methylenebis(cyclohexylamine),
4,4'-methylenebis(2-methylcyclohexylamine), 1,4-diaminocyclohexane, 1,3-cyclohexanebis(methylamine),
1,8-diamino-p-methane, 4,4'-trimethylenedipiperidine, 2-piperidinethanol, 3-piperidinethanol,
4-hydroxypiperidine, 4,4'-trimethylenebis(1-piperidinethanol), 2,2,6,6-tetramethyl-4-piperidinol,
piperazine, 2,6-dimethylpiperazine, 1,4-bis(2-hydroxyethyl)piperazine, homopiperazine,
1,4,7-triazacyclononane, 1,5,9-triazacyclododecane, cyclene, 1,4,8,11-tetraazacyclotetradecane,
1,4,8,12-tetraazacyclotetradecane, 2-anilinoethanol, N-phenyldiethanolamine, 3-aminophenol,
3-aminothiophenol, 4,4'-ethylenedianiline, 3,3'-methylenedianiline, 4,4'-ethylenedianiline,
4-aminophenyl ether, 4-aminophenol, 4-aminophenethyl alcohol, 4,4'-methylenebis(2,6-dimethylaniline),
4,4'-methylenebis(2,6-diehtylaniline), 4,4'-methylenebis(2,6-diisopropylaniline),
3,3',3,5'-tetramethylbenzidine, 1,4-phenylenediamine, N,N'-diphenyl-1,4-phenylenediamine,
2,7-diaminofluorene, N,N'-dibenzylethylenediamine, (±)-syneprine, 4-hydroxy-4-phenylpiperidine,
1,3-bis(phenylphosphino)propane, 1,2-bis(phophino)benzene, 4,4'-isopropylidenedicyclohexanol,
4,4'-(hexafluoroisopropyllidene)diphenol, 4,4'-(1,4-phenylenediisopropylidene)bisphenol
and 1,2-bis(phosphino)ethane.
[0031] The metallocene catalysts are prepared by reacting the metallocene compounds (A)
or (B) with the compounds having at least two functional groups (C), (D) or (E) in
an organic solvent. The molar ratio of transition metal of the metallocene compound
to the compound having at least two functional groups is in the range of 1 : 0.01
∼ 1 : 1000 and preferably 1 : 0.1 ∼ 1 : 20. The reaction temperature is in the range
of -80°C ∼ 300°C and preferably 0°C ∼ 150°C. The weight ratio of an organic solvent
to the reactants is in the range of 0.1 : 1 ∼ 1000 : 1 and preferably 1 : 1 ∼ 100
: 1.
[0032] The metallocene catalyst according to the present invention is employed with a co-catalyst
in order to prepare polystyrene having a syndiotactic structure or polyolefin having
improved physical properties. The co-catalyst is an organometallic compound or a mixture
of non-coordinated Lewis acid and alkylaluminium as is widely known. The organometallic
compound is an alkylaluminoxane or an organoaluminium compound. The representative
examples of alkylaluminoxane are methylaluminoxane (MAO) and modified methylaluminoxane
(MMAO).
[0033] The organoaluminium compound is aluminoxane having the structural unit represented
by the general formula (F). There are aluminoxane having a chain structure represented
by the general formula (G) and aluminoxane having cyclic structure represented by
the general formula (H).
wherein R' is selected from the group consisting of a hydrogen atom; a linear
alkyl group and branched alkyl group of C
1∼10; a cycloalkyl group and a substituted cycloalkyl group of C
3∼20; and an aryl group, an alkylaryl group and an arylalkyl group of C
6∼20; and q is an integer of 0 to 100.
[0034] The olefin or styrene polymerization employs a new metallocene catalyst according
to the present invention and a co-catalyst such as organometallic compound. The component
ratio of the new metallocene catalyst to organometallic compound is the same as the
molar ratio of a transition metal (IV) in the new metallocene catalyst to the aluminium
in the organometallic compound. That is, the molar ratio of the transition metal to
aluminium is in the range of 1 : 1 to 1 : 1 × 10
6 and preferably in the range of 1 : 10 to 1 : 1 × 10
4.
[0035] The co-catalyst used in the present invention is a mixture of non-coordinated Lewis
acid and alkylaluminium. Examples of non-coordinated Lewis acid include N,N-dimethylanilinium
tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)
borate, and ferrocerium tetrakis(pentafluorophenyl)borate. Examples of alkylaluminium
include trimethylaluminium, triethylaluminium, diethylaluminium chloride, triisobutylaluminium,
diisobutylaluminium chloride, diisobutylaluminium hydride, tri(n-butyl)aluminium,
tri(n-propyl)aluminium, and triisopropylaluminium.
[0036] The molar ratio of non-coordinated Lewis acid to a transition metal in the catalyst
system according to the present invention is preferably in the range of 0.1 : 1 ∼
20 : 1. The molar ratio of a transition metal to alkylaluminium in the catalyst system
is preferably in the range of 1 : 1 ∼ 1 : 3000 and more preferably in the range of
1 : 50 ∼ 1 : 1000.
[0037] The reaction temperature for styrene or olefin polymerization by using the catalyst
system according to the present invention is preferably in the range of 0 ∼ 140°C
and more preferably in the range of 30 ∼ 100°C.
[0038] The monomers for polymerization by using the catalyst system according to the present
invention are a styrene, a styrene derivative, or an ethylenically unsaturated compound.
Those monomers can be homopolymerized or copolymerized.
[0039] The styrene and styrene derivative are represented by the general formulae (I) or
(J):
wherein J
1 in the general formula (I) is a hydrogen atom; a halogen atom; or C, O, Si, P, S,
Se or Sn, and m is an integer of 1 to 3, J
1 may be different substituents independently of each other if m is 2 or 3; and J
1 in the general formula (J) is the same as defined in the formula (I), J
2 is a substituent composed of 2 to 10 carbon atoms having at least one unsaturated
bond, m is an integer of 1 to 3, and n is an integer of 1 or 2, in which the benzene
ring may independently have different substituents if m is over 2 and n is 2.
[0040] The illustrative examples of the compounds represented by the general formula (I)
include alkylstyrene, halogenated styrene, halogen-substituted alkylstyrene, alkoxystyrene,
vinylbiphenyl, vinylphenylnaphthalene, vinylphenylanthracene, vinyphenylpyrene, trialkylsilybiphenyl,
trialkylstannylbiphenyl compound, alkylsilystyrene, carboxymethylstyrene, alkylester
styrene, vinylbenzenesulfonic acid ester, and vinylbenzyldialkoxy phosphate.
[0041] The alkylstyrene includes styrene, methylstyrene, ethylstyrene,
n-butylstyrene,
p-methylstyrene,
p-
tert -butylstyrene, and dimethylstyrene.
[0042] The halogenated styrene includes chlorostyrene, bromostyrene, and fluorostyrene.
[0043] The halogenated alkylstyrene includes chloromethylstyrene, bromomethylstyrene, and
fluoromethylstyrene.
[0044] The alkoxystyrene includes methoxystyrene, ethoxystyrene, and butoxystyrene.
[0045] The vinylbiphenyl includes 4-vinylbiphenyl, 3-vinylbiphenyl, and 2-vinylbiphenyl.
[0046] The vinylphenylnaphthalene includes 1-(4-vinylphenylnaphthalene), 2-(4-vinylphenylnaphthalene),
1-(3-vinylphenylnaphthalene), 2-(3-vinylphenylnaphthalene), and 1-(2-vinylphenylnaphthalene).
[0047] The vinylphenylanthracene includes 1-(4-vinylphenylanthracene, 2-(4-vinylphenyl)anthracene,
9-(4-vinyiphenyl)anthracene, 1-(3-vinylphenyl)anthracene, 9-(3-vinylphenyl)anthracene,
and 1-(2-vinylphenyl)anthracene.
[0048] The vinylphenylpyrene includes 1-(4-vinylphenyl)pyrene, 2-(4-vinylphenyl)pyrene,
1-(3-vinylphenyl)pyrene, 2-(3-vinylphenyl)pyrene, 1-(2-vinylphenyl)pyrene, and 2-(2-vinylphenyl)pyrene.
[0049] The trialkyksilyvinylbiphenyl includes 4-vinyl-4-trimethylsilybiphenyl.
[0050] The trialkyistannylbiphenyl includes 4-vinyl-4-trimethylstannylbiphenyl.
[0051] The alkylsilystyrene includes p-trimethylsilystyrene, m-trimethylsilystyrene, o-trimethylsilystyrene,
p-triethylsilystyrene, m-triethylsilystyrene, and o-triethylsilystyrene.
[0052] The illustrative examples of the compounds represented by the general formula (J)
include divinylbenzene such as p-divinylbenzene and m-divinylbenzene; trivinylbenzene;
and aryl styrene such as p-arylstyrene and m-arylstyrene.
[0053] Also, the ethylenically unsaturated monomer is represented by the general formula
(K):
wherein E
1, E
2, E
3 and E
4 are respectively functional groups which are selected the group of a hydrogen atom;
a halogen atom; and substituents containing at least one atom selected from the group
consisting of C, O, Si, P, S, Se and Sn. E
1, E
2, E
3 and E
4 are respectively able to have functional groups which are different from each other.
[0054] The illustrative examples of the compounds represented by the formula (K) are α-olefin,
cyclic olefin, diene, vinylketone, acrolein, acrylonitrile, acryloamide, acrylic acid,
and vinyl acetate.
[0055] Examples of α-olefin include ethylene, propylene, 1-butene, 1-hexene, and 1-octene.
[0056] Examples of cyclic olefin include cyclobutene, cyclopentene, cyclohexene, 3-methylcyclopentene,
3-methylcyclohexene, and norbonene.
[0057] Examples of diene include 1,3-butadiene, isoprene, 1-ethoxy-1,3-butadiene, and chloroprene.
[0058] Examples of vinylketone include methylvinylketone, phenylvinylketone, ethylvinylketone,
and n-propylvinylketone.
[0059] Examples of acrolein include acrolein, and metacrolein.
[0060] Examples of acrylonitrile include vinylidenecyanide, methoxyacrylonitrile, and phenylacrylonitrile.
[0061] Examples of acryloamide include N-methylacryloamide, N-ethylacryloamide, and N-isopropylacryloamide.
[0062] Examples of acrylic acid include aryl acrylate, isopropyl acrylate, ethyl acrylate,
and acrylic acid chloride.
[0063] Examples of vinyl acetate include vinyl acetate and vinyl thioacetate.
[0064] A method of polymerization in accordance with the present invention comprises contacting
monomers selected from the group consisting of styrenes, its derivatives, or ethylenically
unsaturated compounds with the catalyst system according to the present invention.
Monomers, co-catalyst and metallocene catalyst of this invention may be added in a
row to a polymerization reactor. Also, after reacting the metallocene compound and
the compound having at least two functional groups in a polymerization reactor, co-catalyst
and monomers may be added in a row to the polymerization reactor. Further, after reacting
the metallocene compound and the compound having at least two functional groups in
a polymerization reactor being filled with monomers, co-catalyst may be added to the
polymerization reactor. Further, the polymerization may be performed by reacting the
metallocene compound and the compound having at least two functional groups in a reactor
being filled with co-catalyst, aging the resultant solution, and adding the aged solution
to the polymerization reactor being filled with monomers. The resultant solution is
preferably aged at the temperature of 0∼150 °C for 1∼60 min. The copolymerization
of monomers selected from the group consisting of styrenes, its derivatives, ethylenically
unsaturated compounds and a mixture thereof may be carried out as in the polymerization
above.
[0065] The present invention may be better understood by reference to the following examples
which are intended for purposes of illustration and are not to be confined as in any
way limiting the scope of the present invention, which is defined in the claims appended
hereto.
Examples 1 ∼ 18: Synthesis of catalyst
Example 1: catalyst 1
[0066]
[0067] THF (Tetrahydrofuran) 150ml was added to a round-bottomed flask containing 126 mmol
(4.93g) of potassium. After the temperature of the mixture was decreased to 0°C, Cp*(1,2,3,4,5-pentamethylcyclopentadiene)
of 126 mmol (17.17g) was slowly added to the mixture with stirring and then refluxed.
According to proceeding the reaction, white solid was started to be produced. The
mixture was refluxed for 1 hr more since white solid was produced. After the temperature
was again decreased to 0°C, chlorotrimethylsilane of 130 mmol (14.12g) was slowly
added with a syringe. After the mixture was stirred for 2 hrs, it was filtered through
celite to obtain transparent yellowish solution. THF was evaporated under the vacuum
(about 0.1torr) to give a product which trimethylsilane is bonded to Cp*(1,2,3,4,5-pentamethylcyclopentadiene).
The yield was 90%.
[0068] The product which trimethylsilane was bonded to Cp*(1,2,3,4,5-pentamethylcyclopentadiene)
was mixed with toluene of 50ml. The mixed solution was dropwisely added to a round-bottomed
flask containing TiCl
4 of 88.9 mmol (16.86g) and toluene of 200ml with stirring. After the red solution
was stirred for 2 hrs, toluene was evaporated under the vacuum to give a crude solid
product. The crude product was washed with
n-pentane or
n-hexane and dried to obtain the product, that is Cp*TiCl
3 which is a metallocene compound. The yield was 95%.
[0069] Cp*TiCl
3 of 20 mmol (5.79g) was dissolved in THF(100ml). To another round-bottomed flask containing
methanol of 40 mmol (1.28g), THE (100ml) was added. The reaction temperature was decreased
to -78°C with dryice and acetone. After triethylamine of 41 mmol (4.15g) was dropwisely
added to the solution with a syringe, the mixture was stirred for 30 min at -78°C.
To the mixed solution, the Cp*TiCl
3/THF solution was slowly added at -78°C with stirring. The temperature was increased
up to room temperature. After the mixture was stirred for 12 hrs, THF was removed
and hexane of 100ml was added. The solution was stirred for 30 mm and filtered through
celite to give a yellowish solution. The temperature of the yellowish solution was
decreased under -25°C to obtain an orange-colored solid. The precipitated orange-colored
solid was separated from hexane and dried under vacuum to give a product of Cp*TiCl(OCH
3)
2 which two chlorides were substituted with two methoxy groups in Cp*TiCl
3. The yield was 75%.
[0070] Cp*TiCl(OCH
3)
2 of 10 mmol (2.8g) is added to a round-bottomed flask containing THF of 100ml. To
another round-bottomed flask containing 1,6-hexanediol of 5mmol (0.591g), THF (100ml)
was added. The reaction temperature was decreased to -78°C with dryice and acetone.
After triethylamine of 11 mmol (1.11g) was dropwisely added to the solution with a
syringe, the mixture was stirred for 30 min at -78°C. To the mixed solution, the Cp*TiCl(OCH
3)
2/THE solution was slowly added at -78°C with stirring. The temperature was increased
to room temperature. After the mixture was stirred for 12 hrs, THF was removed and
hexane of 100ml was added. The solution was stirred for 30 min and filtered through
celite to give a yellowish solution. After the yellowish solution was evaporated under
vacuum to remove hexane, catalyst 1 was obtained. The yield was 78%.
Example 2: catalyst 2
[0071]
[0072] Catalyst 2 was prepared in the same method as in Example 1 except for using 1,10-decanediol
instead of 1,6-hexanediol.
Example 3: catalyst 3
[0073]
[0074] Catalyst 3 was prepared in the same method as in Example 1 except for using 1,12-dodecanediol
instead of 1,6-hexanediol.
Example 4: catalyst 4
[0075]
[0076] Catalyst 4 was prepared in the same method as in Example 1 except for using 1,4-cyclohexanediol
instead of 1,6-hexanediol.
Example 5: catalyst 5
[0077]
[0078] Catalyst 5 was prepared in the same method as in Example 1 except for using 1,4-decalindiol
instead of 1,6-hexanediol.
Example 6: catalyst 6
[0079]
[0080] Catalyst 6 was prepared in the same method as in Example 1 except for using 4,8-bis(hydroxymethyl)tricyclo[5.2.1.0
2.6]-decane instead of 1,6-hexanediol.
Example 7: catalyst 7
[0081]
[0082] Catalyst 7 was prepared in the same method as in Example 1 except for using 4,4'-isopropylidenediphenol
instead of 1,6-hexanediol.
Example 8: catalyst 8
[0083]
[0084] Catalyst 8 was prepared in the same method as in Example 1 except for using 4,4'-(1,4-phenylenediisopropylidene)bisphenol
instead of 1,6-hexanediol.
Example 9: catalyst 9
[0085]
[0086] Catalyst 9 was prepared in the same method as in Example 1 except for using 2,6-dihydroxynaphthalene
instead of 1,6-hexanediol.
Example 10: catalyst 10
[0087]
[0088] Catalyst 10 was prepared in the same method as in Example 1 except for using 1,5-dihydroxy-1,2,3,4-tetrahydronaphthalene
instead of 1,6-hexanediol.
Example 11: catalyst 11
[0089]
[0090] Catalyst 11 was prepared in the same method as in Example 1 except for using di(ethylene
glycol) instead of 1,6-hexanediol.
Example 12: catalyst 12
[0091]
[0092] Catalyst 12 was prepared in the same method as in Example 1 except for using N-methyldiethanolamine
instead of 1,6-hexanediol.
Example 13: catalyst 13
[0093]
[0094] Catalyst 13 was prepared in the same method as in Example 1 except for using triisopropanolamine
instead of 1,6-hexanediol, and 1/3 equivalent of triisopropanolamine for 1 equivalent
of Cp*Ti(OCH
3)
2Cl.
Example 14: catalyst 14
[0095]
[0096] Catalyst 14 was prepared in the same method as in Example 1 except for using 1,1,1-tris(hydroxymethyl)ethane
instead of 1,6-hexanediol, and 1/3 equivalent of 1,1,1-tri(hydroxymethyl)ethane for
1 equivalent of Cp*Ti(OCH
3)
2Cl.
Example 15: catalyst 15
[0097]
[0098] Catalyst 15 was prepared in the same method as in Example 1 except for using tetraol
instead of 1,6-hexanediol, and 1/4 equivalent of the tetraol compound for 1 equivalent
of Cp*Ti(OCH
3)
2Cl. The tetraol compound was prepared by reacting tetraphenylolethane glycidyl ether
with methylmagnesium bromide.
Example 16: catalyst 16
[0099]
[0100] 20 mmol (5.79g) of Cp*TiCl
3 prepared according to the method of Example 1 was dissolved in THF of 100ml. To another
round-bottomed flask containing methanol of 20 mmol (0.64g), THF (100ml) was added.
The reaction temperature was decreased to -78°C with dryice and acetone. After triethylamine
of 21 mmol (2.08g) was dropwisely added to the solution with a syringe, the mixture
was stirred for 30 mm at -78°C. The resultant solution was slowly added to the Cp*TiCl
3/THF solution at -78°C with stirring. The temperature was increased up to room temperature.
After the mixture was stirred for 12 hrs, THF was removed under
vacuum and hexane of 100ml was added. The solution was stirred for 30 mm and filtered through
celite to give an orange-colored solution. The temperature of the orange-colored solution
was decreased under -25°C to obtain an orange-colored solid. The precipitated orange-colored
solid was separated from
n-hexane and dried under
vacuum to give a product of Cp*TiCl
2(OCH
3) which one chloride was substituted to one methoxy group in Cp*TiCl
3. The yield was 70%.
[0101] Cp*TiCl
2(OCH
3) of 10 mmol (2.8g) was added to a round-bottomed flask containing THF of 100ml. To
another round-bottomed flask containing 1,10-decanediol of 10 mmol (1.743g), THF (100ml)
was added. The reaction temperature was decreased to -78°C with dryice and acetone.
After triethylamine of 22 mmol (2.22g) was dropwisely added to the solution with a
syringe, the mixture was stirred for 30 mm at -78°C. The Cp*TiCl
2(OCH
3)/THF solution was slowly added to the 1,10-decanediol and triethylamine/THF solution
at -78°C with stirring. The temperature was increased up to room temperature. After
the mixture was stirred for 12 hrs, the solution was filtered through celite to give
a yellowish solution. After the yellowish solution was evaporated under
vacuum to remove THF, the catalyst 16 was obtained. The yield was 65%.
Example 17: catalyst 17
[0102]
[0103] After Cp*TiCl
3 was prepared in the method as in Example 1, Cp*TiCl
3 of 20mmol (5.79g) was added to a round-bottomed flask containing toluene of 100ml.
To another round-bottomed flask containing 2,2-Bis(4-hydroxy-3-methylpheyl)propane
30mmol (7.69g), toluene (100ml) was added. After triethylamine of 61mmol (6.17g) was
dropwisely added to the solution with a syringe, the mixture was stirred for 10min
at room temperature. The temperature was decreased to -78°C with dryice and acetone.
The 2,2-Bis(4-hydroxy-3-methylpheyl)propane and triethylamine/toluene solution was
slowly added to the Cp*TiCl
3/toluene solution with stirring at -78°C. After the temperature was increased to room
temperature and the mixed solution was stirred for 15 hrs. The mixed solution was
filtered through celite to give a yellowish solution. After the yellowish solution
was evaporated under vacuum to remove toluene, catalyst 17 was obtained. The yield
was 85%.
Example 18: catalyst 18
[0104]
[0105] Catalyst 18 was prepared in the same method as in Example 17 except for using 4,4'-isopropylidenediphenol
instead of 2,2-Bis(4-hydroxy-3-methylpheyl)propane.
Example 19: styrene polymerization (solution polymerization)
[0106] The styrene polymerization was performed using the new metallocene catalysts 1 ∼
18 prepared in Examples 1 ∼ 18.
[0107] The polymerization reaction was proceeded with a metallocene catalyst having a concentration
(actually, concentration of titanium) of 4×10
-6mol, styrene monomer of 5cc, toluene of 80cc, and a modified methylaluminoxane having
a concentration of aluminium of 1×10
-3mol, for 30 min and at 70°C.
[0108] It was used a temperature-controlling equipment, a magnetic stirrer or a mechanical
stirrer for the styrene polymerization. The polymerization was performed in a glass
reactor with a valve capable of applying monomer and nitrogen gas. After purified
toluene (80cc) was added to the glass flask filled with nitrogen gas instead of air,
the purified styrene (5cc) was again added, and then modified methylaluminoxane (concentration
of aluminium = 1 × 10
-3mol) as a co-catalyst was added with stirring. To the above mixed solution, a certain
amount of a catalyst (concentration of titanium = 4 × 10
-6mol) was added to start polymerizing of the monomer. After the solution was stirred
for a while, a small amount of methanol was added to stop proceeding polymerization.
The obtained mixture was poured into methanol containing hydrogen chloride (HCl) to
give a styrene polymer product. The crude styrene polymer product was washed with
methanol, filtered, and vacuum-dried to obtain a pure styrene polymer. The physical
properties of the polystyrene obtained by polymerization were shown in Table 1.
Table 1
Catalyst (Example) |
Yield (g) |
Activity Kg · PS/[Ti][St]hr |
Stereoregularity (%) |
Molecular weight (× 103) |
Molecular weight distribution |
Melting point (°C) |
Catalyst 1 |
1.95 |
22342 |
97 |
232 |
2.54 |
271 |
Catalyst 2 |
1.97 |
22571 |
98 |
245 |
2.31 |
271 |
Catalyst 3 |
1.97 |
22571 |
98 |
240 |
2.21 |
271 |
Catalyst 4 |
1.96 |
22456 |
97 |
210 |
2.13 |
270 |
Catalyst 5 |
1.93 |
22113 |
96 |
215 |
2.16 |
270 |
Catalyst 6 |
1.94 |
22227 |
97 |
205 |
2.21 |
271 |
Catalyst 7 |
1.87 |
21425 |
98 |
234 |
2.10 |
271 |
Catalyst 8 |
1.91 |
21884 |
98 |
235 |
2.01 |
270 |
Catalyst 9 |
1.90 |
21769 |
97 |
241 |
2.05 |
271 |
Catalyst 10 |
1.95 |
22342 |
98 |
243 |
2.03 |
270 |
Catalyst 11 |
1.30 |
14896 |
95 |
156 |
3.01 |
270 |
Catalyst 12 |
1.42 |
16269 |
95 |
158 |
3.02 |
269 |
Catalyst 13 |
1.65 |
18905 |
96 |
210 |
2.50 |
270 |
Catalyst 14 |
1.60 |
18332 |
96 |
208 |
2.30 |
271 |
Catalyst 15 |
1.35 |
15467 |
95 |
154 |
3.01 |
269 |
Catalyst 16 |
2.01 |
23029 |
97 |
246 |
2.30 |
271 |
Catalyst 17 |
2.81 |
32195 |
99 |
285 |
1.98 |
271 |
Catalyst 18 |
3.02 |
34601 |
99 |
231 |
2.01 |
271 |
Example 20: styrene polymerization (bulk polymerization)
[0109] The styrene polymerization was performed using several catalysts selected from the
group of the new metallocene catalysts 1 ∼ 18 prepared in Examples 1 ∼ 18.
[0110] The polymerization reaction was proceeded with a catalyst having a concentration
(actually, concentration of titanium) of 1.5 × 10
-5mol, styrene monomer of 200cc, triisobutylamine having a concentration of 1.2 × 10
-2mol, and modified methylaluminoxane having a concentration of aluminium of 1.5 × 10
-3mol, for 1 hour and at 70°C.
[0111] A temperature-controlling equipment and a magnetic stirrer or a mechanical stirrer
were used for the styrene polymerization. The polymerization was performed in a glass
reactor with a valve capable of applying monomer and nitrogen gas. After purified
styrene (200cc) was added to a glass flask filled with nitrogen gas instead of air,
and then triisobutylaluminium (1.2 × 10
-2mol) were added. To the resultant solution, modified methylaluminoxane (concentration
of aluminium = 1.5 × 10
-3mol) as a co-catalyst was added with stirring. To the above mixed solution, a certain
amount of a catalyst (concentration of titanium = 1.5 × 10
-5mol) was added to start polymerizing of the monomer. After the solution was stirred
for a while, a small amount of methanol was added to stop proceeding polymerization.
The obtained mixture was poured into methanol containing hydrogen chloride (HCl) to
give a styrene polymer product. The crude styrene polymer product was washed with
methanol, filtered, and vacuum-dried to obtain a pure styrene polymer. The physical
properties of the polystyrene obtained by polymerization are shown in Table 2.
Table 2
Catalyst (Example) |
Yield (g) |
Activity Kg · PS[Ti][St]hr |
Stereoregularity (%) |
Molecular weight (×103) |
Molecular weight distribution |
Melting point (°C) |
Catalyst 2 |
110 |
4200 |
95 |
430 |
2.34 |
271 |
Catalyst 4 |
112 |
4276 |
95 |
421 |
2.31 |
271 |
Catalyst 9 |
115 |
4391 |
96 |
405 |
2.21 |
271 |
Catalyst 16 |
128 |
4887 |
97 |
540 |
2.13 |
272 |
Catalyst 18 |
138 |
5269 |
99 |
534 |
2.21 |
273 |
Example 21: preparation of catalyst and the solution polymerization of styrene in
one reaction container
[0112] A temperature-controlling equipment and a magnetic stirrer or a mechanical stirrer
were used for the styrene polymerization. The polymerization was performed in a glass
reactor with a valve capable of applying monomer and nitrogen gas. The purified toluene
(40cc) was added to a glass flask filled with nitrogen gas instead of air. Pentamethylcyclopentadienyltitaniumtruchloride
[Cp*TiCl
3] of 4 × 10
-6mol (1.16mg) diluted with toluene (20 ml) was added. To the above mixture, the solution
composed of 4,4-isopropylidenediphenol of 6 × 10
-6mol (1.37mg) and triethylamine of 12.05 × 10
-6mol (1.22mg) in toluene of 20 ml was added with stirring. After the mixed solution
was stirred for 1 hour at 100°C, the reaction temperature was decreased to 70°C. Methylaluminoxane
(concentration of aluminium = 1.0 × 10
-3mol) as a co-catalyst was added to the resultant solution with stirring. The purified
styrene (5cc) was added to the solution to start polymerizing and stirred for 30 mm.
A small amount of methanol was added to the solution to stop polymerizing.
[0113] The obtained mixture was poured into methanol containing hydrogen chloride (HCl)
to give a styrene polymer product. The crude styrene polymer product was washed with
methanol, filtered, and vacuum-dried to obtain a pure styrene polymer. The physical
properties of the polystyrene obtained by polymerization are shown in Table 3.
Table 3
Catalyst (Example) |
Yield (g) |
Activity Kg · PS/[Ti][St}hr |
Stereoregularity (%) |
Melting point (°C) |
Catalyst 21 |
2.78 |
31852 |
96 |
271 |
Example 22: preparation of catalyst and the bulk polymerization of styrene in one
reaction container
[0114] A temperature-controlling equipment and a magnetic stirrer or a mechanical stirrer
were used for the styrene polymerization. The polymerization was performed in a glass
reactor with a valve capable of applying monomer and nitrogen gas. After purified
styrene (150cc) was added to a glass flask filled with nitrogen gas instead of air,
pentamethylcyclopentadienyltitanium trichloride [Cp*TiCl
3] of 1.5 × 10
-5mol (4.34mg) diluted with the purified styrene (20cc) was added. To the above mixture,
the solution composed of 4,4'-isopropylidenediphenol of 2.25 × 10
-5mol (5.14mg) and triethylamine of 4.52 × 10
-5mol (4.57mg) in the purified styrene of 30cc was added with stirring. After the mixed
solution was stirred for 5 hours at room temperature, the reaction temperature was
raised up to 70°C. Triisobutylaluminium (1.2 × 10
-2 mol) and methylaluminoxane (concentration of aluminium = 1.5 × 10
-3 mol) as a co-catalyst were added to the resultant solution with stirring to start
polymerizing and stirred for 1 hour. A small amount of methanol was added to the solution
to stop polymerizing. The obtained mixture was poured into methanol containing hydrogen
chloride (HCl) to give a styrene polymer product. The crude styrene polymer product
was washed with methanol, filtered, and vacuum-dried to obtain a pure styrene polymer.
The physical properties of the polystyrene obtained by polymerization are shown in
Table 4.
Table 4
Catalyst (Example) |
Yield (g) |
Activity Kg · PS/(Ti][St)hr |
Stereoregularity (%) |
Catalyst 22 |
135 |
5155 |
99 |
Example 23: modified method for solution polymerization of styrene ( I )
[0115] A temperature-controlling equipment and a magnetic stirrer or a mechanical stirrer
were used for the styrene polymerization. The polymerization was performed in a glass
reactor with a valve capable of applying monomer and nitrogen gas. Purified toluene
(40cc) was added to a glass flask filled with nitrogen gas instead of the air. Pentamethylcyclopentadienyltitanium
trichloride [Cp*TiCl
3], pentarnethylcyclopentadienylmethoxytitanium dichloride (Cp*Ti(OMe)Cl
2], or pentamethylcyclopentadienyldimethoxytitanium chloride [Cp*Ti(OMe)
2Cl] of 4 × 10
-6mol diluted with toluene (20cc) was added to the flask containing the purified toluene
of 40cc. To the above solution, the solution composed of triethylamine and the compound
having at least two functional groups which is represented in the following Table
5 in toluene of 20cc were added with stirring. After the mixed solution was stirred
for 5 hours at room temperature, the reaction temperature was raised up to 70°C. Methylaluminoxane
(concentration of aluminium = 1.0 × 10
-3 mol) as a co-catalyst was added to the resultant solution with stirring. Purified
styrene (5cc) was added to the solution to start polymerizing and stirred for 30 mm.
A small amount of methanol was added to the solution to stop polymerizing.
[0116] The obtained mixture was poured into methanol containing hydrogen chloride (HCl)
to give a styrene polymer product. The crude styrene polymer product was washed with
methanol, filtered, and vacuum-dried to obtain a pure styrene polymer. The physical
properties of the polystyrene obtained by polymerization are shown in Table 5.
Table 5
Half metallocene catalyst (mol) |
Compound having at least two functional groups (mol) |
Mole of N(C2H5)3 |
Yield (g) |
Activity Kg · PS/[Ti][St]hr |
Stereoregularity (%) |
Cp*Ti(OMe)2Cl (4 × 10-6mol) |
1,10-Decandiol (2 × 10-6mol) |
4 × 10-6mol |
1.71 |
19610 |
97 |
Cp*Ti(OMe)Cl2 (4 × 10-6mol) |
1,10-Decandiol (4 × 10-6mol) |
8 × 10-6mol |
1.76 |
20183 |
97 |
Cp*TiCl3 (4 × 10-6mol) |
1,10-Decandiol (6 × 10-6mol) |
12 × 10-6mol |
2.10 |
24083 |
98 |
Cp*TiCl3 (4 × 10-6mol) |
4,4'-Isopropylidenediphenol (6 × 10-6mol) |
12 × 10-6mol |
2.52 |
28899 |
98 |
Example 24: modified method for solution polymerization of styrene (II)
[0117] A temperature-controlling equipment and a magnetic stirrer or a mechanical stirrer
were used for the styrene polymerization. The polymerization was performed in a glass
reactor with a valve capable of applying monomer and nitrogen gas. After purified
toluene (40cc) was added to a glass flask filled with nitrogen gas instead of air,
purified styrene (5 cc) was added. Pentamethylcyclopentadienyltitanium trichioride
[Cp*TiCl
3] pentamethylcyclopentadienylmethoxytitanium dichloride [Cp*Ti(OMe)Cl
2], or pentamethylcyclopentadienydimethoxyltitanium chloride [Cp*Ti(OMe)
2Cl] of 4 × 10
-6mol diluted with toluene (20cc) was added. To the above mixture, the solution composed
of triethylamine and the compound having at least two functional groups which is represented
in the following Table 6 in toluene of 20cc were added with stirring. After the mixed
solution was stirred for 5 hours at room temperature, the reaction temperature was
raised up to 70°C. Methylaluminoxane (concentration of aluminium = 1.0 × 10
-3mol) as a co-catalyst was added to the resultant solution with stirring. After stirred
for 30 min, a small amount of methanol was added to the solution to stop polymerizing.
[0118] The obtained mixture was poured into methanol containing hydrogen chloride (HCl)
to give a styrene polymer product. The crude styrene polymer product was washed with
methanol, filtered, and vacuum-dried to obtain a pure styrene polymer. The physical
properties of the polystyrene obtained by polymerization are shown in Table 6.
Table 6
Half metallocene catalyst (mol) |
Compound having at least two functional groups (mol) |
Mole of N(C2H5)3 |
Yield (g) |
Activity Kg · PS/[Ti][St]hr |
Stereoregularity (%) |
Cp*Ti(OMe)2Cl (4 × 10-6mol) |
1,10-Decandiol (2 × 10-6mol) |
4 × 10-6mol |
1.65 |
18922 |
97 |
Cp*Ti(OMe)Cl2 (4 × 10-6mol) |
1,10-Decandiol (4 × 10-6mol) |
8 × 10-6mol |
1.71 |
19610 |
97 |
Cp*TiCl3 (4 × 10-6mol) |
1,10-Decandiol (6 × 10-6mol) |
12 × 10-6mol |
2.01 |
23050 |
98 |
Cp*TiCl3 (4 × 10-6mol) |
4,4'-Isopropylidene-diphenol (6 × 10-6mol) |
12 × 10-6mol |
2.34 |
26835 |
98 |
Example 25 modified method for solution polymerization of styrene (III)
[0119] A temperature-controlling equipment and a magnetic stirrer or a mechanical stirrer
were used for the styrene polymerization. The polymerization was performed in a glass
reactor with a valve capable of applying monomer and nitrogen gas. After purified
toluene (40cc) was added to a reaction container 1 filled with nitrogen gas instead
of air, purified styrene was added. To another reaction container 2, pentamethylcyclopentadienyltitanium
trichioride [Cp*TiCl
3] and pentamethylcyclopentadienyldimethoxytitanium monochloride [Cp*Ti(OMe)
2Cl] of 4 × 10
-6 mol diluted with toluene (20cc) were added. To the mixed solution in reaction container
2, the solution composed of triethylamine and the compound having at least two functional
groups which is represented in the following Table 7 in toluene of 20cc was added
with stirring. After the mixed solution was stirred for 5 hours at room temperature,
the reaction temperature was raised up to 70°C. Methylaluminoxane (concentration of
aluminium = 1.0 × 10
-3mol) as a co-catalyst was added to the resultant solution with stirring and aged for
10 min. The aged mixed solution in reaction container 2 was added to the reaction
container 1. The obtained mixture was poured into methanol containing hydrogen chloride
(HCl) to give a styrene polymer product. The crude styrene polymer product was washed
with methanol, filtered, and vacuum-dried to obtain a pure styrene polymer. The physical
properties of the polystyrene obtained by polymerization are shown in Table 7.
Table 7
Half metallocene catalyst (mol) |
Compound having at least two functional groups (mol) |
Mole of N(C2H5)3 |
Yield (g) |
Activity Kg · PS/[Ti][St]hr |
Stereoregularity (%) |
Cp*Ti(OMe)2Cl (4 × 10-6mol) |
1,10-Decandiol (2 × 10-6mol) |
4 × 10-6mol |
1.76 |
20183 |
98 |
Cp*TiCl3 (4 × 10-6mol) |
4,4,-4,4'-Isopropylidenediphenol (6 × 10-6mol) |
12 × 10-6mol |
2.36 |
27064 |
98 |
Example 26 : stability test of the catalyst for the air and moisture
[0120] The catalysts 2, 16 and 18 prepared in the same manner as in Examples 2, 16 and 18
were exposed to air for one day. The styrene polymerization was performed in the same
manner as in Example 19 with the air-exposed catalysts. The styrene polymerization
was performed in the same manner as in Example 19 with the catalyst which was not
exposed to the air and moisture. The physical properties of the polystyrenes are shown
in Table 8.
Table 8
Catalyst |
Yield(g) |
Activity Kg · PS/[Ti][St]hr |
Stereoregularity (%) |
Catalyst 2: |
0.89 |
21654 |
97 |
no exposure to the air |
Catalyst 2: |
1.98 |
11228 |
95 |
exposure to the air |
Catalyst 16: |
2.31 |
26467 |
98 |
no exposure to the air |
Catalyst 16: |
1.61 |
18446 |
96 |
exposure to the air |
Catalyst 18: |
2.81 |
32195 |
98 |
no exposure to the air |
Catalyst 18: |
1.93 |
22113 |
96 |
exposure to the air |
Example 27 : copolymerization of styrene with p-methylstyrene
[0121] The polymerization reaction was proceeded with concentration of the catalyst 2, 16
or 18 (concentration of titanium of 4 × 10
-6mol), styrene monomer of 5.44cc,
p-methylstyrene of 0.325cc, toluene of 80cc and concentration of aluminium contained
in modified methylaluminoxanel × 10
-3mol, for 30 mm and at 70°C.
[0122] A temperature-controlling equipment and a magnetic stirrer or a mechanical stirrer
were used for the styrene polymerization. The polymerization was performed in a glass
reactor with a valve capable of applying monomer and nitrogen gas. After purified
toluene (80cc) was added to a glass flask filled with nitrogen gas instead of air,
purified styrene (5.44cc) and
p-methylstyrene (0.325cc) was added, and then modified methylaluminoxane (concentration
of aluminium = 1 × 10
-3mol) as a co-catalyst was added with stirring. To the above mixed solution, a certain
amount of a catalyst (concentration of titanium = 4 × 10
-6mol) was added to start polymerizing of the monomer. After the solution was stirred
for a while, a small amount of methanol was added to stop proceeding polymerization.
The obtained mixture was poured into methanol containing hydrogen chloride (HCl) to
give a styrene polymer product. The crude styrene polymer product was washed with
methanol, filtered, and vacuum-dried to obtain a pure styrene polymer. The physical
properties of the copolymerized styrene obtained by polymerization are shown in Table
9.
Table 9
Catalyst (Example) |
Yield (g) |
Activity Kg · PS/[Ti][St]hr |
Stereoregularity (%) |
Content of monomer (%) |
Tg (°C) |
Tm (°C) |
Catalyst 2 |
2.32 |
23200 |
99 |
7.1 |
100 |
245 |
Catalyst 16 |
2.81 |
28100 |
99 |
7.5 |
101 |
245 |
Catalyst 18 |
3.24 |
32400 |
99 |
8.1 |
99 |
243 |
Example 28 : copolymerization of styrene with divinylbenzene
[0123] The polymerization reaction was proceeded with concentration of the catalyst 2, 16
or 18 (concentration of titanium of 4 × 10
-6mol), styrene monomer of 5cc, divinylbenzene of 0.082cc, toluene of 80cc, and the
modified methylaluminoxane having concentration of aluminium of 1 × 10
-3mol, for 30 min and at 70°C.
[0124] A temperature-controlling equipment and a magnetic stirrer or a mechanical stirrer
were used for the styrene polymerization. The polymerization was performed in a glass
reactor with a valve capable of applying monomer and nitrogen gas. After purified
toluene (80cc) was added to a glass flask filled with nitrogen gas instead of air,
purified styrene (5cc) and divinylbenzene (0.082cc) was added, and then modified methylaluminoxane
(concentration of aluminium = 1 × 10
-3mol) as a co-catalyst was added with stirring. To the above mixed solution, a certain
amount of a catalyst (concentration of titanium = 4 × 10
-6mol) was added to start polymerizing of the monomer. After the solution was stirred
for a while, a small amount of methanol was added to stop proceeding polymerization.
The obtained mixture was poured into methanol containing hydrogen chloride (HCl) to
give a styrene polymer product. The crude styrene polymer product was washed with
methanol, filtered, and vacuum-dried to obtain a pure styrene polymer. The physical
properties of the copolymerized styrene obtained by polymerization are shown in Table
10.
Table 10
Catalyst (Example) |
Yield (g) |
Activity Kg · PS/[Ti][St]hr |
Stereoregularity (%) |
Content of monomer (%) |
Tg (°C) |
Tm (°C) |
Catalyst 2 |
1.64 |
18788 |
99 |
0.9 |
100 |
254 |
Catalyst 16 |
1.76 |
20163 |
99 |
0.9 |
99 |
255 |
Catalyst 18 |
2.02 |
23142 |
99 |
0.9 |
99 |
253 |
Example 29 : copolymerization of styrene with 1,3-butadiene
[0125] The polymerization reaction was proceeded with concentration of the catalyst 2, 16
or 18 (concentration of titanium of 4 × 10
-6mol), styrene monomer of 0.3mol, 1,3-butadiene of 0.30mol, and the modified methylaluminoxane
having concentration of aluminium of 1 × 10
-2mol, for 4 hrs and at 30°C.
[0126] A temperature-controlling equipment and a magnetic stirrer or a mechanical stirrer
were used for the styrene polymerization. The polymerization was performed in a glass
reactor with a valve capable of applying monomer and nitrogen gas. The purified styrene
(0.3mol) and 1,3-butadiene (0.3mol) was added to a glass flask filled with nitrogen
gas instead of air, and then modified methylaluminoxane (concentration of aluminium
= 1 × 10
-2mol) as a co-catalyst was added with stirring. To the above mixed solution, a certain
amount of a catalyst (concentration of titanium = 4 × 10
-6mol) was added to start polymerizing of the monomer. After the solution was stirred
for 4 hours, a small amount of methanol was added to stop proceeding polymerization.
The obtained mixture was poured into methanol containing hydrogen chloride (HCl) to
give a styrene polymer product. The crude styrene polymer product was washed with
methanol, filtered, and vacuum-dried to obtain a pure styrene polymer. The physical
properties of the copolymerized styrene obtained by polymerization are shown in Table
11.
Table 11
Catalyst (Example) |
Yield (g) |
Activity Kg · PS/[Ti][St]hr |
Stereoregularity (%) |
Content of monomer (%) |
Tg (°C) |
Tm (°C) |
Catalyst 2 |
10.89 |
113.4 |
96 |
8.4 |
84 |
267 |
Catalyst 16 |
12.73 |
132.6 |
95 |
8.1 |
86 |
268 |
Catalyst 18 |
13.64 |
142.1 |
96 |
8.6 |
84 |
269 |
[0127] The stereoregularity in Table 1 ∼ 11 was obtained in percent (%) by measuring the
weight of the polymer which was extracted with methyl ethyl ketone, correspondng to
syndiotactic index (S.I.). Also, the syndiotacticity of styrene polymer was measured
with racemic pentad by using
13C-NMR. The glass transition temperature (Tg) and the melting point (Tm) in Table 1
∼ 11 were measured with Differential Scanning Calorimetry (DSC), by heating up to
300°C, resting for 5 min, cooling, and heating the test sample. The rate of temperature
elevation was 10°C/min.
1. A metallocene catalyst for olefin or styrene polymerization prepared by reacting a
metallocene compound represented by the general formula:
MR
1aR
2bR
3cR
44-(a+b+c) (A)
or
MR
1dR
2eR
33-(d+e) (B)
and a compound having at least two functional groups, wherein
M represents a transition metal of Group IV, V or VI of the Periodic Table of Elements;
R1, R2, R3 and R4 are selected from the group consisting of a hydrogen atom; a halogen atom; an alkyl
group, a cycloalkyl group and an alkoxy group of C1-20; an aryl group, an alkylaryl group and an arylalkyl group of C6-20; a cyclopentadienyl group; a substituted cyclopentadienyl group; an indenyl group;
a substituted indenyl group; a fluorenyl group; and a substituted fluorenyl group;
a, b and c are integers from 0 to 4; and
d and e are integers from 0 to 3.
2. The catalyst for olefin or styrene polymerization of claim 1 wherein said compound
having at least two functional groups is represented by the general formula (C):
T
2-YR
5Y'-T
1 (C)
wherein T
1 and T
2 are selected from the group consisting of a hydrogen atom; an alkyl group, a cycloalkyl
group and an alkoxy group of C
1-20; an aryl group, an alkylaryl group and an arylalkyl group of C
6-20; and an alkali metal;
Y and Y' are selected from the group consisting of O, S, -Nr17 and -Pr18, wherein r17 and r18 are selected from the group consisting of a hydrogen atom; an alkyl group, a cycloalkyl
group and an alkoxy group of C1∼10; and an aryl group, an alkylaryl group and an arylalkyl group of C6-20); and
R5 is selected from the group consisting of R', R'-m-R'' or
wherein R', R'', R''' and R'''' are selected from the group consisting of a liner
alkyl group and a branched alkyl group of C6∼20; a cycloalkyl group and a substituted cycloalkyl group of C3∼20 ; or an aryl group, an alkylaryl group and an arylalkyl group of C6∼40; r19 is a hydrogen atom; an alkyl group, a cycloalkyl group and an alkoxy group of C1∼10; or an aryl group, an alkylaryl group and an arylalkyl group of C6∼20; and
m is selected from the group consisting of an oxygen atom, a sulfur atom, -Nr17, -Pr18 and Sir17r18, wherein r17 and r18 are selected from the group consisting of a hydrogen atom; and an alkyl group, a
cycloalkyl group and an alkoxy group of C1-10.
3. The catalyst for olefin and styrene polymerization of claim 1 wherein said compound
having at least two functional groups is represented by the general formula (D):
wherein T
1, T
2 and T
3 are selected from the group consisting of a hydrogen atom; an alkyl group, a cycloalkyl
group and an alkoxy group of C
1-20; an aryl group, an alkylaryl group and an arylalkyl group of C
6-20; and an alkali metal;
Y, Y' and Y'' are selected from the group consisting of O, S, -Nr17 and -Pr18, wherein r17 and r18 are selected from the group consisting of an hydrogen atom; an alkyl group, a cycloalkyl
group and an alkoxy group of C1∼10; and an aryl group, an alkylaryl group and an arylalkyl group of C6-20;
R5, R6 and R7 are selected from the group consisting of R', R'-m-R'' and
wherein R', R'', R''' and R'''' are selected from the group consisting of a linear
alkyl group and a branched alkyl group of C6∼20; a cycloalkyl group and a substituted cycloalkyl group of C3∼20; and an aryl group, an alkylaryl group and an arylalkyl group of C6∼40;
r19 is selected from the group consisting of a hydrogen atom; an alkyl group, a cycloalkyl
group and an alkoxy group of C1∼10; and an aryl group, an alkylaryl group and an arylalkyl group of C6∼20; and
m is selected from the group consisting of an oxygen atom, a sulfur atom, -Nr17, -Pr18 and Sir17r18 , wherein r17 and r18 are selected from the group consisting of a hydrogen atom; an alkyl group, a cycloalkyl
group and an alkoxy group of C1-10; and
Q is N or -Cr20, wherein r20 is selected from the group consisting of an alkyl group, a cycloalkyl group and an
alkoxy group of C1∼10; and an aryl group, an alkylaryl group and an arylalkyl group of C6∼20.
4. The catalyst for olefin and styrene polymerization of claim 1 wherein said compound
having at least two functional groups is represented by the general formula (E):
wherein T
1, T
2, T
3 and T
4 are selected from the group consisting of a hydrogen atom; an alkyl group, a cycloalkyl
group and an alkoxy group of C
1-20; an aryl group, an alkylaryl group and an arylalkyl group of C
6-20; and an alkali metal;
Y, Y', Y'' and Y''' are selected from the group consisting of O, S, -Nr17 and -Pr18, wherein r17 and r18 are selected from the group consisting of a hydrogen atom; an alkyl group, a cycloalkyl
group and an alkoxy group of C1∼10; and an aryl group, an alkylaryl group and an arylalkyl group of C6-20;
R5, R6, R7 and R8 are selected from the group consisting of R', R'-m-R'' and
wherein R', R'', R''' and R'''' are selected from the group consisting of a linear
alkyl group and a branched alkyl group of C6∼20; a cycloalkyl group and a substituted cycloalkyl group of C3∼20; and an aryl group, an alkylaryl group and an arylalkyl group of C6∼40; r19 is a hydrogen atom; an alkyl group, a cycloalkyl group and an alkoxy group of C1∼10; and an aryl group, an alkylaryl group and an arylalkyl group of C6∼20; and
m is selected from the group consisting of an oxygen atom, a sulfur atom, -Nr17, -Pr18 and Sir17 r18, wherein r17 and r18 are selected from the group consisting of a hydrogen atom; and an alkyl group, a
cycloalkyl group and an alkoxy group of C1-10; and
Z is C, Si, Ge or
5. The catalyst for olefin and styrene polymerization of claim 1 wherein said metallocene
compound is selected from the group consisting of pentamethylcyclopentadienyl titanium
trichloride, pentamethylcyclopentadienylmethoxy titanium dichloride, pentamethylcyclopentadienyldimethoxy
titanium monochloride, 1,2,3,4-tetramethylcyclopentadienyl titanium trichloride, 1,2,4-trimethylcyclopentadienyl
titanium trichloride, 1,2-dimethylcyclopentadienyl titanium trichloride, methylcyclopentadienyl
titanium trichloride, cyclopentadienyl titanium trichloride, pentamethylcyclopentadienylmethyl
titanium dichloride, and pentamethylcyclopentadienyldimethyl titanium monochloride.
6. The catalyst for olefin and styrene polymerization of claim 1 wherein said compound
having at least two functional groups is selected from the group consisting of 1,6-hexanediol,
1,12-dodecanediol, 1,4-cyclohexanediol, 1,5-decalinediol, 1,1,1-tris(hydroxymethyl)ethane,
triisopropanolamine, hydroquinone, 2,6-dihydroxynaphthalene, α,α,α',α'-tetramethyl-1,4-benzenedimethanol,
1,5-dihydroxy-1,2,3,4-tetrahydronaphthalene, 4,4'-isopropylidenediphenol, 2,2-bis(4-hydroxy-3-methylphenyl)propane,
meso-hexestrol, 1,6-hexanedithiol, 4,4'-isopropylidenedicyclohexanol, 4,4'-(hexafluoroisopropylidene)diphenol
and 4,4'-(1,4-phenylenediisoprorylidene)bisphenol.
7. The catalyst for olefin and styrene polymerization of claim 1, which is represented
by the general formula (I):
wherein M and M' are transition metals of Group IV, V, and VI of the Periodic Table;
Cp and Cp' are selected from the group consisting of a cyclopentadienyl group, an
indenyl group, a fluorenyl group and a derivative of each group which forms η5-bond with a transition metal such as M and M', and Cp and Cp' are represented by
general formulas (a), (b), (c) and (d);
wherein r1, r2, r3, r4, r5, r6, r7, r8, r9, r10, r11, r12, r13, r14, r15 and r16 are selected from the group consisting of a hydrogen atom; an alkyl group, a cycloalkyl
group and an alkoxy group of C1∼20; and an aryl group, an alkylaryl group and an arylalkyl group of C1∼20; and f is an integer of 4 to 8;
X1, X2, X3 and X4 are selected from the group consisting of a hydrogen atom; a hydroxy group; a halogen
atom; an alkyl group, a cycloalkyl group and an alkoxy group of C1∼20; and an aryl group, an alkylaryl group and an arylalkyl group of C6∼40; and
G is a group connecting between two transition metals and is represented as -YR5Y'- and T2 -YR5Y'-T1, wherein T1 and T2 are selected from the group consisting of a hydrogen atom; and alkyl group, a cycloalkyl
group and an alkoxy group of C1-20; and an aryl group, an alkylaryl group and an arylalkyl group of C6-20; Y and Y' are selected from the group consisting of O, S, -Nr17 and -Pr18, wherein r17 and r18 are selected from the group consisting of a hydrogen atom; an alkyl group, a cycloalkyl
group and an alkoxy group of C1-10; and an aryl group, an alkylaryl group and an arylalkyl group of C6-20); and R5 is R', R'-m-R'' and
wherein R', R'', R''' and R'''' are selected from the group consisting of a linear
alkyl group and a branched alkyl group of C6-20; a cycloalkyl group and a substituted cycloalkyl group of C3-20; and an aryl group, an alkylaryl group and an arylalkyl group of C6-40; and m is selected from the group consisting of an oxygen atom, a sulfur atom, -Nr17, -Pr18 and Sir17r18, wherein r17 and r18 are selected from the group consisting of a hydrogen atom; an alkyl group, a cycloalkyl
group and an alkoxy group of C1-10; and an aryl group, an alkylaryl group and an arylalkyl group of C6∼20.
8. The catalyst for olefin and styrene polymerization of claim 1, which is represented
by the general formula (II):
wherein M, M', X
1, X
4, Cp, Cp' and G are the same as defined in claim 7 and G' is the same as G
9. The catalyst for olefin and styrene polymerization of claim 1, which is represented
by the general formula (III):
wherein M, M', Cp, Cp', G and G' are the same as defined in claim 7 and G'' is the
same as G.
10. The catalyst for olefin and styrene polymerization of claim 1, which is represented
by the general formula (IV):
wherein
M, M', Cp and Cp' are the same as defined in claim 7;
M'' is the same as M;
Cp'' is the same as Cp;
X5 to X10 are the same as X1 in claim 7;
R5 to R7 are selected from the group consisting of a hydrogen atom; an alkyl group of C1∼10; a cycloalkyl group of C3∼20; and an aryl group, an alkylaryl group and an arylalkyl group of C6∼20;
Y, Y' and Y''are selected from the group consisting of O, S, -Nr17 and -Pr18, wherein r17 and r18 are selected from the group consisting of a hydrogen atom; an alkyl group, a cycloalkyl
group and an alkoxy group of C1∼10; and an aryl group, an alkylaryl group and an arylalkyl group of C6∼20; and
Q is N or -Cr20, wherein r20 is selected from the group consisting of a hydrogen atom; an alkyl group, a cycloalkyl
group and an alkoxy group of C1∼10; and an aryl group, an alkylaryl group and an arylalkyl group of C6∼20.
11. The catalyst for olefin and styrene polymerization of claim 1, which is represented
by the general formula (V):
wherein M, M', M'', Cp, Cp', Cp'', X
5 to X
10, R
5 to R
7, Y, Y', and Y'' are the same as defined in claim 10, M''' is the same as M, Cp'''
is the same as Cp, X
8 to X
12 is the same as X
5, R
8 is the same as R
5, Y''' is the same as Y, and
Z is selected from the group consisting of C, Si, Ge and
12. The metallocene catalyst for olefin and styrene polymerization of claim 1 wherein
the molar ratio of said transition metal compound to said compound having at least
two functional groups is from about 1 : 0.2 to about 1 : 100.
13. The catalyst for styrene and olefin polymerization of claim 12 wherein said molar
ratio of said transition metal compound to said compound having at least two functional
groups is from about 1 : 0.25 to about 1 : 5.
14. A catalyst system for styrene and olefin polymerization comprising a catalyst according
to claim 1 and a co-catalyst.
15. The catalyst system of claim 14 wherein said co-catalyst is an organometallic compound.
16. The catalyst system of claim 15 wherein said organometallic compound is selected from
the group consisting of an alkylaluminoxane and an organoaluminium compound.
17. The catalyst system of claim 16 wherein said alkylaluminoxane is methylaluminoxane
or modified methylaluminoxane.
18. The catalyst system of claim 17 wherein said organoaluminoxane compound has the structural
unit represented by the general formula (F), and has a chain and a cyclic structure
represented by the general formulas (G) and (H):
wherein R' is selected from the group consisting of a hydrogen atom; a linear alkyl
group and branched alkyl group of C
1∼10; a cycloalkyl group and a substituted cycloalkyl group of C
3∼20; and an aryl group, an alkylaryl group and an arylalkyl group of C
6∼20: and
q is an integer.
19. The catalyst system of claim 15 wherein the molar ratio of transition metal of said
transition metal compound to aluminium of said organometallic compound is from about
1 : 1 to about 1 : 10000.
20. The catalyst system of claim 19 wherein said molar ratio is from about 1 : 10 to about
1 : 3000.
21. The catalyst system of claim 14 wherein said co-catalyst is a mixture of a non-coordinated
Lewis acid and alkylaluminium.
22. The catalyst system of claim 21 wherein said non-coordinated Lewis acid is selected
from the group consisting of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,
triphenylcarbenium tetrakis(pentafluorophenyl)borate, and ferrocerium tetrakis(pentafluorophenyl)borate.
23. The catalyst system of claim 21 wherein the molar ratio of transition metal of said
catalyst to said non-coordinated Lewis acid is from about 1 : 0.1 to about 1 : 20.
24. The catalyst system of claim 21 wherein said alkylaluminium is selected from the group
consisting of trimethylaluminium, triethylaluminium, diethylaluminium chloride, triisobutylaluminium,
diisobutylaluminium chloride, diisobutylaluminium hydride, tri(n-butyl)aluminium,
tri(n-propyl)aluminium, and triisopropylaluminium.
25. The catalyst system of claim 24 wherein the molar ratio of said transition metal of
said catalyst to said alkylaluminium is in the range of 1 : 1 ∼ 1 : 3000.
26. The catalyst system of claim 25 wherein said molar ratio is from about 1 : 50 to about
1 : 1000.
27. A method of polymerization comprising contacting monomers selected from the group
consisting of styrene, derivatives of styrene, and ethylenically unsaturated compounds
with the catalyst system according to claim 14.
28. The method of claim 27 wherein said monomers, co-catalyst and the metallocene catalyst
of claim 1 are added sequentially to a polymerization reactor.
29. The method of claim 27 wherein said step of contacting monomers comprises reacting
the metallocene compound and the compound having at least two functional groups of
claim 1 in a polymerization reactor and adding co-catalyst and monomers sequentially
to the polymerization reactor.
30. The method of claim 27 wherein said step of contacting monomers comprises reacting
the metallocene compound and the compound having at least two functional groups of
claim 1 in a polymerization reactor being filled with monomers and adding co-catalyst
to the polymerization reactor.
31. The method of claim 27 wherein said step of contacting monomers comprises reacting
the metallocene compound and the compound having at least two functional groups of
claim 1 in a reactor being filled with co-catalyst, aging the resultant solution,
and adding the aged solution to the polymerization reactor being filled with monomers.
32. The method of claim 31 wherein said resultant solution is aged at the temperature
of 0 ∼ 150 °C for from about 1 to about 60 minutes.
33. A method of copolymerization comprising contacting monomers selected from the group
consisting of styrene, derivatives of styrene, ethylenically unsaturated compounds
and a mixture thereof with the catalyst system according to claim 14.
34. The method of claim 33 wherein said monomers, co-catalyst and the metallocene catalyst
of claim 1 are added sequentially to a polymerization reactor.
35. The method of claim 33 wherein said step of contacting monomers comprises reacting
the metallocene compound and the compound having at least two functional groups of
claim 1 in a polymerization reactor and adding co-catalyst and monomers sequentially
to the polymerization reactor.
36. The method of claim 33 wherein said step of contacting monomers comprises reacting
the metallocene compound and the compound having at least two functional groups of
claim 1 in a polymerization reactor being filled with monomers and adding co-catalyst
to the polymerization reactor.
37. The method of claim 33 wherein said step of contacting monomers comprises reacting
the metallocene compound and the compound having at least two functional groups of
claim 1 in a reactor being filled with co-catalyst, aging the resultant solution,
and adding the aged solution to the polymerization reactor being filled with monomers.
38. The method of claim 37 wherein said resultant solution is aged at the temperature
of from about 0 to 150 °C for about 1 to about 60 minutes.